EP4342580A1 - 1,3-butadiensynthesekatalysator, verfahren zur herstellung davon und verfahren zur herstellung von 1,3-butadien - Google Patents

1,3-butadiensynthesekatalysator, verfahren zur herstellung davon und verfahren zur herstellung von 1,3-butadien Download PDF

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Publication number
EP4342580A1
EP4342580A1 EP21951876.8A EP21951876A EP4342580A1 EP 4342580 A1 EP4342580 A1 EP 4342580A1 EP 21951876 A EP21951876 A EP 21951876A EP 4342580 A1 EP4342580 A1 EP 4342580A1
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EP
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Prior art keywords
catalyst
butadiene
producing
silica support
ethanol
Prior art date
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Pending
Application number
EP21951876.8A
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English (en)
French (fr)
Inventor
Norihiko Nakamura
Noritatsu Tsubaki
Guohui YANG
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Toyo Tire Corp
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Toyo Tire Corp
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Publication of EP4342580A1 publication Critical patent/EP4342580A1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11

Definitions

  • Embodiments of the present invention relate to a catalyst for synthesizing 1,3-butadiene from ethanol, a method for producing the same, and a method for producing 1,3-butadiene using the catalyst.
  • 1,3-Butadiene is widely used as a raw material in the production of butadiene rubber (BR) and styrene-butadiene rubber (SBR).
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • 1,3-butadiene is mainly produced by separation from the C4 fraction resulting from the production of ethylene by steam-cracking naphtha.
  • a synthesis method in which ethanol is directly converted into 1,3-butadiene has been proposed.
  • a catalyst containing a zeolite material having a YO 2 -containing framework structure, in which at least part of Y contained in the framework structure is isomorphously substituted with element X has been disclosed.
  • Y is preferably Si, Sn, Ti, Zr, or Ge
  • X is preferably Zr, Ti, Sn, or Ta.
  • a zeolite material in which Y is Si, and X is Ti may further contain Zn as a non-framework element.
  • Direct conversion of ethanol into 1,3-butadiene is a promising route.
  • the direct conversion is a complex reaction, requiring multifunctional catalysts having dehydrogenation sites, Lewis acid sites, and mild Bronsted sites.
  • the yield of 1,3-butadiene is not necessarily high, and an improvement in the yield has been demanded.
  • An object of some embodiments of the invention is to provide a catalyst for 1,3-butadiene synthesis, which is capable of efficiently synthesizing 1,3-butadiene from ethanol, a method for producing the same, and a method for producing ethanol using the catalyst.
  • the invention includes the following embodiments.
  • 1,3-butadiene can be efficiently synthesized from ethanol.
  • catalysts for 1,3-butadiene synthesis (hereinafter sometimes simply referred to as a "catalyst") according to this embodiment and a method for producing 1,3-butadiene using the same will be described.
  • a catalyst according to an embodiment is a catalyst for synthesizing 1,3-butadiene from ethanol and contains a porous silica support, Zn, and Zr.
  • the silica support is made of crystalline silica, which is porous crystalline with a three-dimensional pore structure. Therefore, compared to a support composed of amorphous silica, the specific surface area is larger, which is advantageous for the dispersion of various active centers, allowing for an improvement in catalyst performance.
  • pores micropores, mesopores, and macropores can be mentioned.
  • the silica support may have only one of them, or may also have two or more kinds.
  • micropores refer to pores having a pore size of 2 nm or less.
  • Mesopores refer to pores having a pore size of more than 2 nm and less than 50 nm.
  • Macropores refer to pores having a pore size of 50 nm or more.
  • the silica support has a framework structure containing SiO 2 .
  • the framework structure is basically composed of SiO 2 , but Si contained in the framework structure may be partially substituted with a trivalent, tetravalent, and/or pentavalent element such as aluminum. It is preferable that the silica support has an SiO 2 framework structure without such substitution.
  • the silica support may be a zeolite containing no elemental aluminum (i.e., dealuminated zeolite).
  • the framework structure of the silica support is not particularly limited, and, for example, MFI type, BEA type, FER type, MWW type, MOR type, FAU type, LTA type, LTL type, and the like can be mentioned.
  • the silica support may have one of them, or may also have a combination of two or more kinds of framework structures. Among them, a silica support in one embodiment preferably has an MFI-type framework structure.
  • ZnO zinc
  • the ZnO supported on the silica support is believed to mainly promote the dehydrogenation of ethanol.
  • zirconium (Zr) is contained mainly in the state of having been interacted with silanol groups (Si-OH) of the silica support. Because the atomic radius of Zr is larger than that of Si, Zr does not enter the framework structure of the silica support in the course of catalyst synthesis. Zr interacts with silanol groups on the SiO 2 surface within pores of the silica support, forming Lewis active centers.
  • the interaction between silanol groups and Zr means the formation of any bond between silanol groups and Zr.
  • Zr may have entirely interacted with silanol groups as described above, but it is also possible that Zr is partially supported on the silica support in the form of an oxide, that is, ZrO 2 .
  • Zr may be contained in the form of Zr(OH)(OSi) 3 and ZrO 2 .
  • the catalyst according to this embodiment has at least one kind of pores selected from the group consisting of micropores, mesopores, and macropores.
  • the catalyst preferably has micropores with a pore size of 2 nm or less.
  • mesopores and/or macropores may also be present together with micropores.
  • the pore size of micropores the peak pore size in the HK pore size distribution is preferably, but not particularly limited to, 0.3 nm or more and 1.5 nm or less, and more preferably 0.5 nm or more and 1.0 nm or less.
  • the molar ratio Zn/Si of elemental zinc to elemental silica is not particularly limited, but is preferably 0.001 to 0.1.
  • the molar ratio Zn/Si is 0.001 or more, the promoting effect on the dehydrogenation of ethanol can be enhanced.
  • the molar ratio Zn/Si is 0.1 or less, the dehydrogenation of ethanol can be promoted without inhibiting the action of other active species.
  • the molar ratio Zn/Si is preferably 0.005 or more, and more preferably 0.008 or more.
  • the molar ratio Zn/Si is preferably 0.05 or less, and more preferably 0.03 or less.
  • the molar ratio Zr/Si of elemental zirconium to elemental silica is not particularly limited, but is preferably 0.05 to 0.5.
  • the molar ratio Zr/Si is 0.05 or more, the promoting effects on aldol condensation and MPV reduction can be enhanced.
  • the molar ratio Zr/Si is 0.5 or less, the generation of by-products can be suppressed.
  • the molar ratio Zr/Si is preferably 0.08 or more, and more preferably 0.1 or more.
  • the molar ratio Zr/Si is preferably 0.4 or less, and more preferably 0.3 or less.
  • the method for producing the above catalyst is not particularly limited, but preparation by a hydrothermal synthesis method is preferable.
  • Zinc salts are not particularly limited, and, for example, water-soluble zinc salts such as zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, and zinc bromide can be mentioned. One of them may be used alone, and it is also possible to use a combination of two or more kinds.
  • Zirconium alkoxides are not particularly limited, and, for example, zirconium methoxide, zirconium ethoxide, zirconium propoxide, zirconium butoxide, and the like can be mentioned. One of them may be used alone, and it is also possible to use a combination of two or more kinds.
  • Template agents are not particularly limited, and it is preferable to use tetrapropylammonium hydroxide (TPAOH), for example.
  • TPAOH tetrapropylammonium hydroxide
  • TEOS tetraethoxysilane
  • TEMOS tetramethoxysilane
  • tetrapropoxysilane tetrabutoxysilane, and the like
  • One of them may be used alone, and it is also possible to use a combination of two or more kinds.
  • the amount of zinc salt used is not particularly limited, but is preferably such that, relative to the amount of orthosilicic acid ester used, the molar ratio Zn/Si of elemental zinc to elemental silicon is 0.001 to 0.1, more preferably 0.005 to 0.05, and still more preferably 0.008 to 0.03.
  • the amount of zirconium alkoxide used is not particularly limited, but is preferably such that, relative to the amount of orthosilicic acid ester used, the molar ratio Zr/Si of elemental zirconium to elemental silicon is 0.05 to 0.5, more preferably 0.08 to 0.4, and still more preferably 0.1 to 0.3.
  • the amount of template agent used is not particularly limited, and may be, per 100 parts by mass of the amount of orthosilicic acid ester used, 20 to 200 parts by mass, 50 to 150 parts by mass, or 80 to 120 parts by mass.
  • step (i) when a zinc salt, a zirconium alkoxide, an orthosilicic acid ester, a template agent, and water are mixed, other components such as lower alcohols may also be contained.
  • step (i) it is possible that a zinc salt, a zirconium alkoxide, and an orthosilicic acid ester are dissolved in a lower alcohol such as ethanol, and a template agent and water are added to the resulting solution and mixed.
  • a template agent and water are added to the resulting solution and mixed.
  • step (i) the lower alcohol may be distilled off from the ZnZr silicate precursor-containing mixture thus obtained.
  • step (ii) hydrothermal synthesis is performed using the mixture.
  • Hydrothermal synthesis is a reaction performed in the presence of high-temperature, highpressure hot water, and further dehydration condensation takes place to produce silica.
  • pores having a predetermined pore size are formed.
  • the zinc salt and the zirconium alkoxide are mixed together with the orthosilicic acid ester, and subjected to one-pod hydrothermal synthesis, the active centers Zn and Zr can be uniformly dispersed in the silica support, promoting the interaction between active centers.
  • Hydrothermal synthesis can be performed using an autoclave, for example.
  • the treatment conditions are not particularly limited, and the treatment may be performed, for example, at 150 to 180°C for 24 to 96 hours under a pressure spontaneously generated due to volume expansion.
  • the resulting reaction product is dried, and then, in step (iii), the reaction product is calcined.
  • the calcination temperature is not particularly limited and may be, for example, 300 to 700°C, or 400 to 600°C. If necessary, calcination may be followed by pulverization and further molding, such as particle sizing.
  • the method for producing 1,3-butadiene according to this embodiment includes obtaining 1,3-butadiene from ethanol in the presence of the catalyst according to this embodiment described above. For this purpose, a raw material containing ethanol needs to be brought into contact with the above catalyst.
  • the synthesis route from ethanol to 1,3-butadiene using the catalyst is not particularly limited, but is generally believed to be as follows. That is, (1) ethanol undergoes dehydrogenation to form acetaldehyde, (2) acetaldehyde undergoes aldol condensation to form acetaldol, (3) acetaldol undergoes a dehydration reaction to form crotonaldehyde, (4) crotonaldehyde undergoes MPV reduction together with ethanol to form crotyl alcohol, and (5) crotyl alcohol undergoes dehydration to form 1,3-butadiene.
  • the ethanol used in the production is not particularly limited and may be, for example, bioethanol produced from biomass, or may also be ethanol synthesized through a hydration reaction of fossil fuel-derived ethylene, etc.
  • the above raw material may also contain other components such as acetaldehyde.
  • the method for bringing a raw material containing ethanol into contact with the catalyst is not particularly limited as long as the method can convert ethanol into 1,3-butadiene in the presence of the catalyst, and the contact may be made in the gas phase or in the liquid phase. It is preferable that the raw material containing ethanol is used as a gas, and the gas is passed through a catalyst bed containing the catalyst to cause a reaction in the gas phase.
  • the raw material gas may be fed to the reaction system without being diluted, or also may be fed after being diluted with an inert gas such as nitrogen or argon.
  • the reaction temperature (catalyst bed temperature) is not particularly limited as long as it is a temperature that can convert ethanol into 1,3-butadiene, and may be, for example, 250 to 500°C, or 300 to 400°C.
  • the reaction pressure is not particularly limited either and may be, for example, from atmospheric pressure to 1 MPa.
  • the reaction mode may be a continuous flow type or a batch type.
  • the weight hourly space velocity (WHSV) which is the ratio of the raw material feed rate (weight/hour) to the catalyst weight, is not particularly limited and may be, for example, 0.1 to 10 h -1 , or 0.3 to 2 h -1 .
  • the reaction form is not particularly limited and may be a fixed-bed type, a moving-bed type, or a fluidized-bed type.
  • the form of the reactor is not particularly limited either, and tubular reactors and the like can be used, for example.
  • the obtained product may be subjected to purification, such as distillation, if necessary.
  • purification such as distillation, if necessary.
  • unreacted ethanol and by-products such as ethylene, ether, and acetaldehyde can be removed.
  • N 2 adsorption/desorption was measured using "3Flex 2MP" manufactured by Micromeritics as the measuring apparatus.
  • the sample was degassed under vacuum at 3 50°C for 5 hours.
  • This measuring apparatus analyzes the pore size distribution of micropores by the HK method, while analyzes the pore size distribution of mesopores and that of macropores by the BJH method.
  • the pore size distribution of the Log differential pore volume distribution (dV/dlogD) was determined by the measurement, and, from the obtained pore size distribution, the peak pore size was determined.
  • 0.05 g of zinc acetate (Zn(CH 3 COO) 2 ⁇ 2H 2 O) and 5.21 g of tetraethoxysilane (TEOS) were added to 10 mL of ethanol and dissolved by stirring for 1 hour.
  • 2.40 g of zirconium butoxide (Zr(OBu) 4 ) was added thereto and stirred for 1 hour, and then 5.08 g of tetrapropylammonium hydroxide (TPAOH) and 18.69 g of water were added and mixed by stirring for 4 hours.
  • the resulting mixed solution was heated at 90°C for 4 hours to distill off ethanol, then transferred to a fluorine resin-lined stainless steel autoclave, and subjected to hydrothermal synthesis at 130°C for 48 hours under a pressure spontaneously generated due to volume expansion.
  • the obtained ZnZrMFI catalyst had a peak pore size of 0.54 nm and had micropores.
  • the ZnZrMFI catalyst was subjected to X-ray photoelectron spectroscopy (XPS) analysis using an Al Ka X-ray source.
  • XPS X-ray photoelectron spectroscopy
  • the Zn 2p spectrum shown in Fig. 1 and the Zr 3d spectrum shown in Fig. 2 were obtained.
  • the crystal structure of the ZnZrMFI catalyst was analyzed using the X-ray diffraction (XRD) method (CuK ⁇ 40 kV, 20 mA, 6° to 60°), and the measurement results shown in Fig. 3 were obtained.
  • XRD X-ray diffraction
  • the ZnZrMFI catalyst (Zn 0.01 Zr 0.2 MFI(mi)) exhibits higher binding energies of Zr 3d peaks than pure ZrO 2 , showing that a chemical species different from ZrO 2 was formed.
  • the two peaks of the ZnZrMFI catalyst can be divided into two main peaks and two weak peaks. The two weak peaks whose binding energies match the peaks of pure ZrO 2 correspond to ZrO 2 , and the two main peaks that have shifted to higher energies correspond to Si-O-Zr.
  • the ZnZrMFI catalyst (Zn 0.01 Zr 0.2 MFI(mi)) has peaks peculiar to MFI, which are indicated by "x".
  • the prepared ZnZrMFI catalyst contains a silica support having an MFI-type framework structure, Zn is supported on the silica support in the form of ZnO, and Zr is contained in the form of Zr(OH)(OSi) 3 and ZrO 2 .
  • CAB cetyltrimethylammonium bromide
  • Each catalyst prepared above was subjected to a catalyst performance evaluation test through a 1,3-butadiene synthesis reaction from ethanol.
  • the synthesis reaction was performed under atmospheric pressure using a fixed-bed flow reactor made of quartz with an inner diameter of 4 mm.
  • FIG. 4 The conceptual diagram of the reaction apparatus is as shown in Fig. 4 .
  • reference numeral 12 indicates a nitrogen cylinder that feeds nitrogen as a carrier gas
  • reference numeral 14 indicates a syringe pump that feeds ethanol
  • reference numeral 16 indicates a mass flow controller (MFC)
  • reference numeral 18 indicates an evaporator
  • reference numeral 20 indicates a ribbon heater for line heating, which heats the outer periphery of a tube through which the gas flows.
  • MFC mass flow controller
  • Reference numeral 22 indicates a fixed-bed flow-type reactor
  • reference numeral 24 indicates a catalyst bed within the reactor
  • reference numeral 26 indicates an electric furnace that heats the reactor
  • reference numeral 28 indicates a thermocouple thermometer (TC) that detects the temperature of the catalyst bed 24.
  • TC thermocouple thermometer
  • Reference numeral 30 indicates a tube through which the gas that has passed through the reactor 22 flows
  • reference numeral 32 indicates a bypass route that bypasses the reactor 22
  • reference numeral 34 indicates a gas chromatograph (GC) for analyzing gas products
  • reference numeral 36 indicates an exhaust gas outlet
  • reference numeral 38 indicates a six-way valve for switching the flow path for the tube 30, the bypass route 32, the GC 34, and the exhaust gas outlet 36.
  • GC gas chromatograph
  • 0.5 g of a catalyst was packed in the reactor 22 to form a catalyst bed 24, and the catalyst bed 24 was filled with quartz wool 40 at both ends and fixed.
  • Nitrogen was passed from the nitrogen cylinder 12 through the MFC 16 into the reactor 22 at a flow rate of 20 mL/min to perform a pretreatment at 400°C for 1 hour.
  • the gas product emitted from the reactor 22 was introduced to the gas chromatograph (GC) 34 on line, and the gas products were analyzed using a gas chromatograph ("Shimadzu GC-14B" manufactured by Shimadzu Corporation and "DB-1 Column (30 m ⁇ 0.25 mm ⁇ 0.25 ⁇ m)" manufactured by GL Sciences Inc.) and a flame ionization detector (FID).
  • a gas chromatograph (“Shimadzu GC-14B" manufactured by Shimadzu Corporation and "DB-1 Column (30 m ⁇ 0.25 mm ⁇ 0.25 ⁇ m)" manufactured by GL Sciences Inc.) and a flame ionization detector (FID).

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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
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EP21951876.8A 2021-07-29 2021-07-29 1,3-butadiensynthesekatalysator, verfahren zur herstellung davon und verfahren zur herstellung von 1,3-butadien Pending EP4342580A1 (de)

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PCT/JP2021/028199 WO2023007676A1 (ja) 2021-07-29 2021-07-29 １，３－ブタジエン用合成触媒及びその製造方法、並びに１，３－ブタジエンの製造方法

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US9878965B2 (en) * 2013-06-13 2018-01-30 Basf Se Process for the preparation of butadiene
WO2014199348A2 (en) * 2013-06-13 2014-12-18 Basf Se Metal doped silicate catalysts for the selective conversion of ethanol to butadiene
CN109894144B (zh) * 2017-12-07 2021-08-17 中国科学院大连化学物理研究所 一种1,3-丁二烯的合成方法及其催化剂的制备方法

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